CN103562149A

CN103562149A - Method for surfactant crystal growth of a metal-nonmetal compound

Info

Publication number: CN103562149A
Application number: CN201280019383.6A
Authority: CN
Inventors: 摩西·艾纳夫
Original assignee: Mosaic Crystals Ltd
Current assignee: Mosaic Crystals Ltd
Priority date: 2011-03-04
Filing date: 2012-03-04
Publication date: 2014-02-05
Also published as: JP2014508415A; WO2012120497A1; AU2012226395A1; US20130333613A1; CA2829064A1; US8945302B2; WO2012120497A4; EP2688847A1; KR20140024303A; BR112013022384A2

Abstract

A method for crystal growth from a surfactant of a metal-nonmetal (MN) compound, includes the procedures of providing a seed crystal, introducing atoms of a first metal to contact with the seed crystal thus forming a thin liquid metal wetting layer on a surface of the seed crystal, setting a temperature of the seed crystal below a minimal temperature required for dissolving MN molecules in the wetting layer and above a melting point of the first metal, each one of the MN molecules being formed from an atom of a second metal and an atom of a first nonmetal, introducing the MN molecules which form an MN surfactant monolayer, thereby facilitating a formation of the wetting layer between the MN surfactant monolayer and the surface of the seed crystal, and regulating a thickness of the wetting layer, thereby growing an epitaxial layer of the MN compound on the seed crystal.

Description

The method of growing for the tensio-active agent crystal of metal-nonmetallic compound

The field of disclosed technology

Disclosed technology relates in general to crystal growth, and in particular to the method and system that uses the crystal of tensio-active agent growing metal-nonmetallic compound.

The background of disclosed technology

In this area, being used for is known from the method for liquid melts growing crystal.For example, the U.S. Patent No. 7,097,707 that the title of giving Xu is " GaN boule grown from liquid melt using GaN seed wafers " relates to the method for the preparation of monocrystalline GaN boule.First method is included in the program that makes GaN seed wafer contact GaN source environment under processing condition.Processing condition are included in the growth for produce gan on GaN seed wafer of thermal gradient in the environment of GaN source, thereby form GaN boule.In the supercritical ammine of the GaN that source environment can be selected from gallium melt and nitrogenous source or contain dissolving.

Second method is included in the program that nitrogenous source exists and gallium melt is provided under thermal gradient and GaN seed wafer is contacted with gallium melt.This is created in the growth of gan on GaN seed wafer, thereby forms GaN boule.GaN seed wafer is connected to rotatable bar.During GaN boule-grown, from gallium melt, in pull lever and GaN seed wafer, rotate rotatable bar, thereby rotation GaN seed wafer.Nitrogenous source comprises nitrogen plasma, and described nitrogen plasma comprises Nitrogen Atom, nitrogen ion and phenodiazine ion.Same surrounding environment is formed by gallium melt and GaN seed wafer.By being selected from the discharge technology of direct-current discharge, radio frequency discharge and microwave discharge, produce nitrogen plasma.The temperature of gallium melt is approximately 900 ℃ to approximately 1500 ℃.By the reaction between nitrogenous source and gallium melt, at gallium bath surface, form GaN hard formation (crust).Thermal gradient is included in temperature higher on GaN hard formation than in GaN Seed Layer, via the Nitrogen Atom of dissolving in gallium melt, gan is transported in the growth of the gan on GaN seed wafer by hard formation thus.On described hard formation, at described temperature, the GaN in hard formation is degraded into the Nitrogen Atom with equilibrium concentration.The equilibrium concentration of Nitrogen Atom is oversaturated with respect to the temperature of GaN seed wafer, thereby on seed wafer, produces the isoepitaxial growth of GaN.

The U.S. Patent No. 7,892,513 that the title of giving Fuiiwara etc. is " Group III nitride crystal and method of its growth " relates to growing method.Said method comprising the steps of: preparation has the substrate of major surfaces, and at least in its main surface side, comprises the III-th family nitride crystal seed with the chemical constitution identical with III-th family nitride crystal.Mean density along the threading dislocation (threading dislocations) of major surfaces is 5x10 ⁶cm ^-2or lower.Described method also comprises that making wherein nitrogenous gas be dissolved in containing the solution of III-th family metal solvent and the major surfaces of substrate contacts, so that III-th family nitride crystal grows to the step of the major surfaces of substrate.

The summary of disclosure technology

The object of disclosed technology is to provide novel method and the system for growing from staying in the crystal of the tensio-active agent growing high-quality metal-nonmetallic compound crystal thin liquid metal wetting layer.According to disclosed technology, thereby be provided for from the method for the crystal growth of the tensio-active agent of metal-nonmetal (MN) compound, described method comprise the atom that crystal seed is provided and introduces the first metal to contact with crystal seed to form the program of thin liquid metal wetting layer at least one surface of crystal seed.Described method also comprises the Temperature Setting of crystal seed for lower than dissolving the required minimum temperature of MN molecule in the liquid metal wetting layer thin and higher than the program of the fusing point of the first metal.Each MN molecule forms by least one bimetallic atom and at least one the first nonmetallic atom.Described method also comprises the program of introducing the MN molecule that forms MN tensio-active agent individual layer, thereby promotes to form thin liquid metal wetting layer between MN tensio-active agent individual layer and seed surface.Described method finally comprises the program of the thickness that regulates thin liquid metal wetting layer, makes MN molecule and the seed surface coupling of at least some MN tensio-active agent individual layers, thus the epitaxial film of the MN compound of growing on crystal seed.

According to disclosed technology on the other hand, thereby be provided for from the method for the tensio-active agent crystal growth of metal-nonmetal (MN) compound, described method comprises to be provided crystal seed and near crystal seed, is introducing the atom of the first metal to form the program of thin liquid metal wetting layer at least one surface at crystal seed.Described method also comprises the Temperature Setting of crystal seed for lower than dissolving the required minimum temperature of MN molecule in the liquid metal wetting layer thin and higher than the program of the fusing point of the first metal.Each MN molecule forms by least one bimetallic atom and at least one the first nonmetallic atom.Described method also comprises the program of introducing the MN molecule that forms MN tensio-active agent individual layer, thereby promotes to form thin liquid metal wetting layer between MN tensio-active agent individual layer and seed surface.Described method finally comprises that the thickness of the liquid metal wetting layer that adjusting is thin makes at least some MN molecules and the seed surface coupling of MN tensio-active agent individual layer, thus the program of the epitaxial film of the MN compound of growing on crystal seed.

According to the another aspect of disclosed technology, thereby be provided for from the system of the tensio-active agent crystal growth of the metal from metal melt-nonmetal (MN) compound, described system comprises growth room, pedestal and motor.Pedestal is positioned at inside, growth room.Motor and pedestal couple and at growth room's mobile foundation.Crystal seed is placed on pedestal, makes the growth surface of crystal seed face the direction back to pedestal.Growth room is full of metal melt growth surface is covered by the thin layer of metal melt.Introduce nonmetal gas to the growth room on the surface of metal melt.Nonmetal gas particle and metal melt particle interaction, thus MN tensio-active agent individual layer formed.Distance between growth regulation surface and MN tensio-active agent individual layer makes molecule tunnelling in MN tensio-active agent individual layer to growth surface, thus on growth surface at least one crystal layer of epitaxy.

According to disclosed technology on the other hand, thereby be provided for from the system of the tensio-active agent crystal growth of the metal from film-nonmetal (MN) compound, described system comprises growth room, the first gas inlet and the second gas inlet.The first gas inlet and growth room couple and for introducing metal vapors to growth room.The second gas inlet and growth room couple and for introducing nonmetal steam to growth room.Crystal seed is placed in to growth room.Growth room is full of metal vapors and nonmetal steam simultaneously, make metal vapors and nonmetal steam codeposition on the growth surface of crystal seed, thereby form the MN tensio-active agent individual layer on thin liquid metal wetting layer and thin liquid metal wetting layer from metal vapors.The concentration of metal vapors makes to form thin liquid metal wetting layer higher than the concentration of nonmetal steam at first.Regulate the thickness of thin liquid metal wetting layer to make MN molecule tunnelling in MN tensio-active agent individual layer to growth surface, thus on growth surface at least one crystal layer of epitaxy.

Accompanying drawing summary

By following detailed description, together with accompanying drawing, will understand more completely and know from experience disclosed technology, wherein:

Fig. 1 is for according to the schematic diagram of the method for disclosed technology exercisable crystal from tensio-active agent growing metal-nonmetallic compound of embodiment;

Fig. 2 A uses the first schematic diagram that builds the atomic structure of metal-nonmetallic compound crystal of growing with the method for exercisable Fig. 1 according to another embodiment of disclosed technology;

Fig. 2 B uses the second schematic diagram that builds the atomic structure of metal-nonmetallic compound crystal of growing with the method for exercisable Fig. 1 according to the another embodiment of disclosed technology;

Fig. 2 C uses the 3rd schematic diagram that builds the atomic structure of metal-nonmetallic compound crystal of growing with the method for exercisable Fig. 1 according to another embodiment of disclosed technology;

Fig. 2 D uses the 4th schematic diagram that builds the atomic structure of metal-nonmetallic compound crystal of growing with the method for exercisable Fig. 1 according to the another embodiment of disclosed technology;

Fig. 3 A uses according to another embodiment of disclosed technology to build the schematic diagram with the system of method growing metal-nonmetallic compound crystal of exercisable Fig. 1;

Fig. 3 B uses according to the another embodiment of disclosed technology to build the schematic diagram with another system of method growing metal-nonmetallic compound crystal of exercisable Fig. 1;

Fig. 4 A builds the schematic diagram with exercisable epitaxially grown crystal according to another embodiment of disclosed technology;

Fig. 4 B builds and the exercisable schematic diagram that shows the epitaxially grown crystal of Manhattan (Manhattan) structure according to the another embodiment of disclosed technology; And

Fig. 4 C builds and the exercisable schematic diagram that shows the epitaxially grown crystal of nano thread structure according to another embodiment of disclosed technology.

The detailed description of embodiment

Disclosed technology is by being provided for overcoming the deficiencies in the prior art from staying in the novel crystal growth method of metal-nonmetallic compound crystal of the tensio-active agent growing high-quality on thin liquid metal wetting layer.According to disclosed technology, thin liquid metal wetting layer has non-metallic atom or the metal-nonmetal particle that is insoluble to thin liquid metal wetting layer.Non-metallic atom and particle are combined and are adsorbed on the upper surface of thin liquid metal wetting layer with atoms metal and the particle of thin liquid metal wetting layer, thereby form and comprise the tensio-active agent individual layer that has thin metal side and have a liking for the metal-nonmetal molecule of the specific orientation of metal side.When by the metal of tensio-active agent individual layer-nonmetallic molecule with will be grown as crystal seed when next-door neighbour of crystal, physical mechanism make the metal-nonmetallic molecule of described tensio-active agent individual layer can transition, tunnelling or diffusion and with crystal seed coupling.Repeatedly this type of transition will form the epitaxial film of metal-nonmetal molecule on crystal seed, thereby increases its volume and remarkable growing metal-nonmetallic compound crystal on crystal seed.Distance between crystal seed in growth regulation and the upper strata of thin liquid metal wetting layer continues supplying metal-nonmetal molecule in tensio-active agent individual layer, will epitaxy crystal seed to metal-nonmetallic compound crystal.

Disclosed technology relates to for the general method of crystal growth and is limited to from the crystal of compound-material growth.Generally speaking, use the crystal of disclosed technology growth from comprising at least one metal and at least one nonmetallic precursor compound (abridge in this article and be called MN compound) growth.In the description of disclosed technology, term ' metal ' is classified as any element of basic metal, alkaline-earth metal, transition metal, lanthanon, actinide elements or other metal for representative element periodictable.In the description of disclosed technology, term ' nonmetal ' is classified as any element of nonmetal or halogen for representative element periodictable, such as hydrogen (H), boron (B), carbon (C), nitrogen N), oxygen (O), silicon (Si), phosphorus (P), sulphur (S), arsenic (As), selenium (Se), antimony (Sb), tellurium (Te), fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).The example that can be used as the MN compound of precursor compound comprises gan (GaN), aluminum oxide (Al ₂o ₃), selenizing zinc chrome (CdZnSe), indium gallium nitride (InGaN), spinel (MgAl ₂o ₄), yttrium barium copper oxide (YBa ₂cu ₃o ₇) etc.

With reference now to according to the exercisable schematic diagram Fig. 1 for the method from tensio-active agent growing metal-nonmetallic compound crystal of the embodiment of disclosed technology.In program 100, provide crystal seed.Crystal seed represent disclosed technology MN compound crystal by thereon growth substrate.Crystal seed can have crystallography structure and the orientation and limited never in any form of any kind.The example that different crystal is learned structure is shown in figure below 4A-4C.In addition, crystal seed can be used to the homogeneous crystal of growing, and the element that wherein comprises the element of crystal seed and comprise MN compound is substantially similar.Crystal seed also can be used to the heterocrystal of growing, and the element that wherein comprises the element of crystal seed and comprise MN compound is substantially different.Seed can also be the little crystallite that can be one of a plurality of polycrystalline seeds of growing in amorphous or crystalline substrate.According to disclosed technology, multiple growing environment is possible and depends on specific for grown MN compound crystal.In addition, as described belowly according to disclosed technology, can in selected growing environment, use known growing method such as chemical vapour deposition (being abbreviated as CVD herein), molecular beam epitaxy (being abbreviated as MBE herein), rheotaxy (being abbreviated as LPE herein), vapour phase epitaxy (being abbreviated as VPE herein) etc. to introduce the required precursor substance of growth MN compound crystal.Therefore,, in program 100, according to by grown specific MN compound crystal and selected for introducing the method for required precursor substance, the crystal seed providing is placed in suitable growing environment substantially.As the first example, in crystal seed can being provided in program 100 and being placed on crucible with deposite metal, such as using in solution growth or LPE.As the second example, crystal seed can be provided in program 100 and it is placed in to high vacuum chamber as wafer, such as using in MBE.As the 3rd example, can provide crystal seed as the multiple sublayer being deposited in crystalline texture or on amorphous structure.

In program 102, near crystal seed, introducing the atom of the first metal to form thin liquid metal wetting layer at least one surface of crystal seed.In the alternative form of program 102, the atom of introducing the first metal contacts with crystal seed to form thin liquid metal wetting layer at least one surface of crystal seed.As mentioned above, the first metal can be similar or be different from the metal in crystal seed.In addition, the first metal can be different from metal in crystal seed and by the metal in grown MN crystal.In this respect, the metal of the thin liquid metal wetting layer of formation can be different from metal in crystal seed and according to disclosed technology as the metal in the metal-nonmetal molecule of the precursor substance of growth MN crystal.Generally speaking, as the solvent inferior of MN molecule, the first metal may have particular community such as low melting glass, high evaporation temperature, and described MN molecule will deposit as MN crystal on crystal seed.The example of the first metal can comprise mercury (Hg), gallium (Ga), zinc (Zn), tin (Sn), magnesium (Mg) etc.In this program, any currently known methods in this area all can be used for introducing the atom of the first metal.For example, when be placed in Michel Knuysen (Knudsen) container using the first atoms metal as solid, with container described in post-heating, take and distil the atom of the first metal during as steam, can using the first atoms metal as the most at last at least one surface of crystal seed condensing steam introduce.Also the atom of the first metal can be introduced as the liquid metal (being metal melt) that surrounds crystal seed on its one of surface at least.Should point out can be in program 102 the first atoms metal to be introduced as the compound that comprises metallic element and non-metallic element, wherein compound near crystal seed, be dissociated thereby discharge the non-metallic atom of compound and on crystal seed by the first atoms metal condensing be liquid.Also should point out to select the crystal seed for program 100, make can when not dissolving crystal seed, with liquid state, be present on the surface of crystal seed near the atom of the first metal being introduced into crystal seed, the atom of described the first metal finally forms thin liquid metal wetting layer at least one surface of crystal seed.

In program 104, set the temperature of crystal seed lower than the required minimum temperature of dissolution of metals-nonmetal molecule in the liquid metal wetting layer thin.This temperature can be called as liquidus temperature.As mentioned above, disclosed technology relates to the MN compound crystal of growing on crystal seed.According to selected, will be grown as the metal-nonmetallic compound of crystal, set the temperature of crystal seed lower than liquidus temperature but still higher than the fusing point that forms the first atoms metal of thin liquid metal wetting layer.Should point out in an embodiment of disclosed technology, above-mentioned metal-nonmetal molecule forms the atom by least one the first metal and at least one first nonmetallic atom.Therefore the metal of, mentioning in the metal in this program-nonmetal molecule is substantially the same with the metal of the thin liquid metal wetting layer that comprises program 102.For example, if will be in program 100 on crystal seed growing gallium nitride (being abbreviated as GaN herein) crystal, then in program 102, near crystal seed, introduce gallium (Ga) atom, or introduce gallium (Ga) atom with contact crystal seed, thereby finally on the surface of crystal seed, form thin liquid gallium wetting layer.In program 104, set the temperature of crystal seed lower than liquidus temperature, described temperature will be lower than 1150 ℃ in this example.Generally speaking, according to they phasors separately, unless known MN compound under very high temperature and/or very high pressure, MN compound is not soluble in the liquid melts of the metal that forms MN compound.

According to another embodiment of disclosed technology, above-mentioned metal-nonmetal molecule will be formed by least one bimetallic atom and at least one first nonmetallic atom.Therefore the metal of, mentioning in the metal-nonmetal molecule of this program and comprise that the metal of thin liquid metal wetting layer of program 102 is substantially different.As mentioned above, the first metal and the second metal in this embodiment, mentioned can be different from the metal that forms crystal seed.According to embodiment before, silicon carbide (being abbreviated as SiC herein) crystal (also referred to as silicon carbide) can be grown from thin liquid-state silicon wetting layer (wherein the temperature of crystal seed will be set to higher than 1400 ℃).According to this embodiment, SiC can grow from thin liquid tin wetting layer (wherein the temperature of crystal seed will be set to about 250 ℃).This embodiment can be used for growing crystal of many other types, such as quartzy, rutile (TiO ₂) etc.

In program 106, introduce the molecule of MN compound to the growing environment of crystal seed.Can introduce MN compound as the molecule of metal and nonmetal bonding wherein.Can carry out this introducing by evaporation MN compound, gasification MN precursor or sputter MN compound target.Also can introduce MN compound as independent metal and nonmetal particle (such as atom, ion, group etc.), described metal and nonmetal particle in growing environment in conjunction with to form MN molecule.Should point out in the introducing of this second type, metal and nonmetal particle are by codeposition together with forming the metal of MN molecule, and the first metallographic phase of introducing in the metal of described formation MN molecule and program 102 together.For example, when steering routine 106 in simultaneous other optional procedure, can in the growing environment of crystal seed, the first nonmetallic atom gasification be made these first non-metallic atoms be combined with the first atoms metal of program 106 thereby the thin liquid metal wetting layer that forms on crystal seed on form MN molecule and MN tensio-active agent individual layer.Generally speaking, thus tensio-active agent refers to the surface tension that reduces liquid to be sprawled liquid and improves class soap (soap-like) substrate of wetting situation.During the given seed surface of MN molecules strike, MN molecule starts to form thin metal-nonmetallic surface promoting agent individual layer on thin liquid metal wetting layer surface.Generally speaking, only when being introduced into the atoms metal of growing environment, just can form thin liquid metal wetting layer when more than non-metallic atom.As known in the art, if only MN molecule be introduced into growing environment and provide to seed, will on crystal seed, there is the growth of steam solid crystal.This MN layer is the individual layer of the thickness of a molecule of MN compound substantially.MN individual layer also shows two dimensional crystal shape structure, wherein said individual layer comprise be present in the upper surface of thin liquid metal wetting layer and on this on the repeating structure of the MN molecule that substantially flattens.Molecule self in this MN layer builds to form tensio-active agent, and wherein atoms metal points to and to face the direction of thin liquid metal wetting layer and non-metallic atom points to the back of the body towards the direction of thin liquid metal wetting layer.In figure below 2A-2C, show this point in greater detail, wherein show MN tensio-active agent individual layer comprise face thin liquid metal wetting layer have a liking for metal side and the back of the body towards the thin metal side of thin liquid metal wetting layer.

MN tensio-active agent individual layer promotes to be substantially formed at the formation of liquid metal wetting layer thin between MN tensio-active agent individual layer and given seed surface.In this respect, within the metal of MN tensio-active agent partly faces thin liquid metal wetting layer, and the non-metallic part of MN tensio-active agent deviates from liquid metal wetting layer.Owing to setting the temperature of crystal seed, make the MN molecule of introducing will be insoluble to thin liquid metal wetting layer as whole molecule, the MN molecule of introducing is adsorbed on the upper surface of thin liquid metal wetting layer substantially as tensio-active agent individual layer.MN tensio-active agent individual layer makes thin liquid metal wetting layer flatten substantially.

In program 108, regulate the thickness of thin liquid metal wetting layer to make at least some MN molecules in MN tensio-active agent individual layer and given seed surface coupling, thus the epitaxial film of the MN compound of growing on crystal seed.According to disclosed technology, for example, if thin liquid metal wetting layer is thin (several nanometer thickness) substantially, the MN molecule in MN tensio-active agent individual layer substantially can from tensio-active agent individual layer directly ' transition ', ' tunnelling ' or ' diffusion ' to crystal seed and with crystal seed coupling, thereby another individual layer of the MN compound of growing on crystal seed.Generally speaking, the MN molecule in tensio-active agent individual layer be added in simultaneously crystal on crystal seed grow required specific thicknesses or thickness range depend on select as the metal of MN compound and nonmetal, for selection, the crystal seed temperature of the metal of thin liquid metal wetting layer and introduce metal and nonmetal precursor elements or compound to tensio-active agent individual layer energy used.Therefore, on crystal seed as every type of the MN compound of crystal growth, in this program, need to regulate specific thicknesses or thickness range so that the enough precursor substances that acts on the MN crystal of growing on crystal seed of the MN molecular energy of MN tensio-active agent individual layer.If it is too thin that thin liquid metal wetting layer becomes, wetting layer will parch and the successively epitaxy of crystal will stop.If it is too thick that thin liquid metal wetting layer becomes, ' transition ', ' tunnelling ' or ' diffusion ' to crystal (growing crystal) and the crystal growth in growth simultaneously of the MN molecule in tensio-active agent individual layer will stop completely.

In program 108, according to how to introduce, form respectively the metal of thin liquid metal wetting layer and MN tensio-active agent individual layer and non-metallic atom to growing environment, can regulate by various technology the thickness of thin liquid metal wetting layer.For example, if use evaporator crucible to introduce MN molecule, can regulate MN molecular flow via the evaporation controller of controlling evaporation of metal speed in program 106.Can specialize the evaporation controller in this type of environment of crystal growth via the vibration piezoelectric quartz crystal coupling with proportion integration differentiation (being abbreviated as PID herein) controller.If the MN molecule in program 106 is introduced as plasma body via at least one gas inlet, can regulate with gas inlet pressure warning unit the amount of the plasma body that enters growing environment.Then can measure and in growing environment, have which plasma species and their relative density with spectrophotometer.Only have some plasma species will contribute to MN tensio-active agent individual layer.

According to another embodiment of disclosed technology, do not using under gas inlet pressure warning unit and/or spectrophotometer and can carry out adjusting to entering the amount of the plasma body of growing environment.In this embodiment, can use as follows drop standard (droplet criterion).Generally speaking, if be introduced in growing environment MN molecule as plasma body, between metal that need to be in being introduced into growing environment and nonmetallic substance, reach specific stoichiometry trim point.At this trim point, the ratio of metal and nonmetallic substance be the molecule that thin liquid metal wetting layer had make in MN tensio-active agent individual layer can with the thickness that grows in the crystal coupling on crystal seed.Generally speaking, at single layer crystal growing period, on the surface of the crystal that the drop of specific precursor substance can be in growth, form.Use the example of growing gan crystal, along with using, with the plasmatron of high power operation, introduce nitrogen plasma in growing environment, speed that can be stable is using Ga as gas evaporation.Amorphous or the polycrystalline material that then can use refletcion high-energy electron diffraction (being abbreviated as RHEED herein) technology for detection to grow on seed surface, described amorphous or polycrystalline material will manifest as high-intensity spots on RHEED monitor.When reducing the power of plasmatron, the image on RHEED monitor by the luminous point of the darker record simultaneously that becomes still less.Finally, will not have luminous point to be recorded and under this plasma body tube power level Ga drop beginning is formed on seed surface.By using trial and error pricing (trial and error), can further reduce and improve plasmatron power level, make not have drop to form on seed surface.When not having droplet-shaped to be formed on seed surface, reach above-mentioned trim point, make thin liquid metal wetting layer start to form on seed surface.Other trial and error pricing method may be for measuring the suitable amount of metal and nonmetal particle, for obtaining thin liquid metal wetting layer and MN tensio-active agent individual layer.

Mention backhaul order 104, the exact temperature that crystal seed is set to depends on many factors, and described factor can be measured in order to form metal and the non-metallic atom of MN compound by trial and error pricing and according to selecting.For example, the temperature of crystal seed need to be introduced into higher than at least one the fusing point of the metal of MN compound.Because metal mixture can have lower than the eutectic melting point that forms the single metal fusing point of mixture, should point out whether this temperature is introduced into the metal that depends on introducing as pure metal or metal mixture.Higher temperature on melting point metal can be increased in the sedimentation rate of the lip-deep atoms metal of MN tensio-active agent individual layer, thereby molecule deposition speed or ' the tunnelling speed ' of the crystal in the growth increasing from tensio-active agent individual layer to crystal seed.Even higher temperature (although lower than minimum temperature of describing in program 104) can increase extremely such speed of tunnelling speed: described speed can receive publicity when regulating the metal of formation MN compound and the stoichiometric balance point of nonmetal particle.In addition,, at this type of higher temperature, the MN molecule of the crystal during the MN molecule of formation tensio-active agent individual layer can evaporate and grow can dissociate from the current grown layer of crystal.As known in the art, use trial and error pricing can measure the optimum temps of crystal seed, wherein the speed that is incorporated to of MN molecule is maximized, yet the stoichiometric balance point of metal and nonmetal precursor substance can be conditioned.Because the two-forty of introducing can increase epitaxy, betide the speed on crystal seed, also should point out that trial and error pricing can be used to measure by those skilled in the art to introduce the first atoms metal and the first non-metallic atom to the speed (according to above program 102 and 106) in growing environment.Yet meanwhile, too high introducing speed can make to be difficult to keep the stoichiometric balance point between metal and nonmetal precursor substance.

Should point out that the method for describing in Fig. 1 is different from substantially from temperature (growth of crystal is possible under described temperature) other art methods of lower growth from solution crystal substantially.For example, temperature that conventionally need to be up to 1400 ℃ for the art methods from growth from solution GaN crystal and the pressure of 15000 bar, wherein can be low to moderate growing gan crystal under the temperature of 35 ℃ and vacuum condition according to disclosed technology.The art methods of growth spinel is used the temperature up to 2140 ℃, and can be low to moderate the spinel of growing at the temperature of 450 ℃ according to disclosed technology.Because thermal potential mistake when the crystal of at high temperature growth is cooled to available temperature such as room temperature can occur, the growth of crystal can increase the quality of the crystal of growth substantially at low temperatures.According to disclosed technology, by reducing the temperature gap between growth temperature and use temperature, substantially can reduce thermal potential mistake.

After program 108, can carry out the first atoms metal of wherein no longer supplying in program 102 to the other program of growing environment.Due to the termination of the first atoms metal in growing environment, the thin liquid metal wetting layer forming in program 106 by parch and program 108 in crystal seed on the successively epitaxy of MN compound crystal will stop.Because the temperature of crystal seed will be dissolvable in water the temperature in thin liquid metal wetting layer lower than MN molecule, as known in technique, any crystal growth of the metal-nonmetallic compound on crystal seed will occur according to the technology of steam solid growth under low temperature.The epitaxially grown MN compound crystal that the steam solid growth of the crystal on crystal seed shows flat single crystal structure by change is the crystal that shows polycrystalline structure.Polycrystalline structure can be regarded as can repeating now the new crystal seed of the crystal technique of Fig. 1 substantially thereon.Therefore,, after this other program, the method for Fig. 1 can be back to the extension of program 102 and MN compound crystal and successively grow and can again recover.Should point out can to grow the in this way different layers of MN compound crystal, wherein every layer by different metals and/or nonmetally form.Also should point out if the former crystal seed of program 100 has taper geometry, make to grow nano-pillar (shown in following Fig. 4 C) from crystal seed, when forming polycrystalline structure in this other program, polycrystalline structure also can show thereon according to can grow to the extension taper geometry of other nano-pillar of the method in Fig. 1.Should point out when thin liquid metal wetting layer is become dry, can change the temperature of crystal seed in growing environment and the sedimentation rate of any metal and/or nonmetal particle with the polycrystalline crystal layer of growth particular type, described polycrystalline crystal layer cushions between the polycrystal layer of the connection of epitaxial crystal growth.For example, before forming new thin liquid metal wetting layer, can significantly increase metal and/or nonmetallic sedimentation rate so that growth is flat and thick polycrystalline crystal layer.

After program 108, can after above-mentioned other program or as the alternative form of above-mentioned other program, carry out another program.In this another program, being supplied to substantially of the first nonmetal particle of can slowing down gradually do not have, thereby rather than stop supplies the first atoms metal is in growing environment and thin liquid metal wetting layer is parched, thereby on the surface of the crystal of growth, leave the thin layer of the first atoms metal.Then this thin layer can maybe can be used known wet-chemical or plasma chemistry technology to etch away by the evaporation of heating crystal seed.Remove this thin layer and will cause carrying out the clean upper surface of crystal of the growth of other technique thereon.If grow and there is the crystal of Manhattan structure or the crystal of nano-pillar form (being shown in figure below 4B and 4C) by the method for Fig. 1, after this another program, can clean the crystal of growth or the upper surface of nano-pillar by technology listed above, thereby leave the crystal of growth and/or the clean upper surface of nano-pillar.Any kish staying between the crystal of growing and/or nano-pillar also can be by evaporation or via using known wet-chemical or the etching of plasma chemistry technology remove.

With reference now to the first schematic diagram Fig. 2 A of atomic structure that uses metal-nonmetallic compound crystal of the method growth in Fig. 1 of the general reference 150 that builds and operate according to another embodiment of disclosed technology.Fig. 2 A comprises solid phase 152, thin liquid metal wetting layer 154, MN tensio-active agent individual layer 156 and gas phase 158.Generally speaking, Fig. 2 A-2C is presented at after steering routine 100-106 (Fig. 1), at the top of crystal seed, forms the atomic structure after thin liquid metal wetting layer and MN tensio-active agent individual layer.Crystal seed can be solid phase 152 or solid phase 152 descend part.Crystal 153 in solid phase 152 representative growths.In this schematic diagram, shown the GaN crystal that comprises a plurality of Ga atoms 160 and a plurality of N atoms 162.And select GaN that disclosed technology is described as an example, thereby because its structure is relatively simple and graphical format is simple, and the MN compound that the method that the general atomic structure of describing in Fig. 2 A-2C is applicable to show in any use Fig. 1 is grown as crystal.As shown in the crystal 153 in growth, a plurality of Ga atoms 160 and a plurality of N atom 162 are arranged in crystallography structure.The lower level (not shown) of the crystal 153 in growth can represent on it grows and has the crystal seed (not shown) of the crystal 153 in growth.As mentioned above, crystal seed can with growth in crystal 153 homogeneous or heterogeneous.For example crystal seed can be GaN seed, sapphire seed or silicon seed.In addition,, if the crystal 153 in growth is sapphires, crystal seed can be sapphire seed or silicon seed.In the situation that the crystal 153 in crystal seed and growth is heterogeneous, the number due to the crystal misfit dislocation that the difference of crystallography structure causes separately (misfit dislocations) in crystal seed and growth is the inverse that is exposed to the seed sized of growth substantially.Therefore the crystal seed of reduced size that, is exposed to growth is by the misfit dislocation on the crystal causing in less growth (when both are heterogeneous).

Described in following Fig. 4 A-4C, crystal seed (not shown) can have any suitable possible geometry that makes epitaxial crystal growth.For example, crystal seed can have flat geometrical shape, and traditional successively extension wherein can occur, as shown at this Fig. 2 A-2C and figure below 4A.As another example, following Fig. 4 C is shown, and crystal seed can have taper geometry, can be from the nano-pillar of growing crystal wherein.Crystal seed can be also the prior seed of crystallization seed or the huge mm size of nano-scale.Crystal seed can also be to have at least one flat surperficial wafer or the tip of crystalline fibers.Also point out crystal seed can with crystalline material (not shown) or the coupling of amorphous substance (not shown).A requirement of crystal seed is that it does not dissolve or be melted in and can surround (not shown) in the thin liquid metal wetting layer 154 of solid phase 152 or metal melt.Also any crystallographic orientation that can select crystal seed is for the growth of the crystal 153 in growth, and it is parallel with the direction of thin liquid metal wetting layer 154 that precondition is the orientation selected.

Following Fig. 3 A and 3B are described in more detail, and thin liquid metal wetting layer 154 is represented as the metal of a part for the MN crystal on crystal seed.As shown in Figure 2 A, although the Ga atom in thin liquid metal wetting layer 154 does not form a part for solid phase 152, thin liquid metal wetting layer 154 comprises a plurality of Ga atoms 160.Following Fig. 3 A describes, and in fact thin liquid metal wetting layer 154 can be a part of surrounding the metallic solution (not shown) of crystal seed.Metallic solution can be the mixture of metal.In this case the ratio of metallic solution composition should be corresponding to the mol ratio of metal mixture so that crystal can grow.For example,, if metallic solution is only to comprise that the spinel solution of the metal part of spinel (is that spinel has MgAl ₂o ₄chemical formula, MgAl wherein ₂represent the metal part of spinel), according to the chemical formula solution of spinel, should there is the mol ratio of 1 magnesium (Mg), 2 aluminium of atomic ratio (Al) atom.This example shows compared with prior art for the crystal of the disclosed technology temperature required difference of growing.Use MgAl ₂o ₄pure spinel solution come growing crystal need to produce spinel melt.The fusing point of spinel is 2135 ℃, thereby needs high temperature to produce spinel melt and to cause difficulty in the crystal growth in hot environment like this.The metal mixture of magnesium and aluminium has the eutectic melting point of 425 ℃, thereby makes to use lesser temps substantially to become possibility to produce the metallic solution of disclosed technology.In addition,, if use crucible, the temperature of growing environment has also determined the type of the crucible material that uses and in order to generate the type of the well heater of metallic solution.Lesser temps makes to use more kinds of crucible materials and well heater and has higher price-performance ratio.

Generally speaking, as above Fig. 1 describes, and uses various known technologies such as evaporation of vapours, MBE, CVD, VPE etc., and thin liquid metal wetting layer 154 can be deposited on the crystal 153 in growth.Although in this technology, should be noted that sputtering technology also can be used for thin liquid metal wetting layer 154 to be deposited on the crystal 153 in growth about the purity of thin liquid metal wetting layer and the sedimentation rate on its crystal 153 in growth.Following Fig. 3 A and 3B are shown, and thin liquid metal wetting layer can be metal melt on the crystal being formed in crystal seed or growth or a part for film.Although crystal seed can be placed in to metal melt according to some embodiment of disclosed technology, be different from the method for prior art crystal growth, do not need crystal seed (can be wafer) to immerse in metal melt.Generally speaking, when supply atom and particle are in the growing environment of the crystal 153 in growth time, as the precursor metal of the crystal 153 in growth and non-metallic atom and particle, will be introduced in growing environment by codeposition simultaneously.This codeposition makes the epitaxy of the crystal 153 in growth become possibility.Although be not shown in clearly in Fig. 2 A, according to the different metal mixture of disclosed technology, to pass in time and can be introduced in growing environment, each mixture is deposited to produce the crystal in the growth of the composition with different layers with its speed separately.

Following Fig. 3 A and 3B describe, can be with being used as the system of a large amount of crystal growths or by the system for the growth of thin film epitaxy crystal, the crystal 153 of growth being grown.In either case, the nonmetal composition of the crystal in growth 153 carrys out the shown gas of gas phase 158 freely.As shown in Fig. 2 A, gas phase 158 comprises a plurality of N atoms 162.According to how introducing N atom to growing environment, in fact the N atom in gas phase 158 can be the various materials of N particle, such as ion or group.The specific nonmetallic various systems that are introduced into are depended in use, can supply the nonmetal particle of gas phase 158 to growing environment.Nonmetal particle can pure form be introduced into or be introduced into as the part of mixture or the compound that dissociates in growing environment.For example, if will introduce oxygen in gas phase 158, can provide oxygen from oxygen container.If will introduce boron in gas phase 158, can provide Decaboron tetradecahydride, described Decaboron tetradecahydride is activated by plasma body or ruptures when it clashes into MN tensio-active agent individual layer 156.If will introduce carbon in gas phase 158, can provide suitable hydrocarbon such as methane, described methane is activated by plasma body or ruptures when its clashes into MN tensio-active agent individual layer 156.May be by silane (SiH ₄) with acting on the precursor substance of introducing silicon in gas phase 158, and non-metallic element such as P, As, Sb, S, Se and Te by can introduce the V HeVI family with low melting point from crucible evaporation is to the growing environment of gas phase 158.Can gas phase 158, introduce nitrogen from nitrogen gas container or as ammonia.Also can be using nitrogen as nitrogen plasma or the ammonia of fracture introduce.Generally speaking, if nonmetal particle is introduced in gas phase 158 as the gaseous compound (such as at approximately 750 ℃ of ammonias that dissociate) with relatively high dissociation temperature, radio frequency (being abbreviated as RF herein) plasma body or electron cyclotron resonace (being abbreviated as ECR herein) plasma body can be used to supply active nonmetal particle.In other cases, can be the enough high any gaseous compound to dissociate in gas phase 158 of the temperature of thin liquid metal wetting layer 154.Also as shown in Fig. 2 A and Fig. 2 B and 2C, according to disclosed technology, crystal 153 in growth is grown in can being regarded as ' rich metallic ' growing environment, and thin liquid metal wetting layer 154 comprises than the more metallics of the nonmetal particle in gas phase 158.

As shown in Fig. 2 A, MN tensio-active agent individual layer 156 form the top of thin liquid wetting metal layer 154 and represent gas phase 158 and thin liquid metal wetting layer 154 between interface.MN tensio-active agent individual layer 156 is included in a plurality of MN molecules that form two-dimentional liquid crystal on the surface of thin liquid metal wetting layer 154.As shown in the example of Fig. 2 A, MN tensio-active agent individual layer 156 comprises a plurality of GaN molecule 1s 66, comprises a GaN molecule 1 68 and the 2nd GaN molecule 1 70 for the illustrative order in Fig. 2 A-2C, selected.As shown in dotted line 164, a plurality of GaN molecule 1s 66 substantially make the upper surface of thin liquid metal wetting layer 154 flatten and are organized as the structure of the two-dimensional crystal lattice of self-assembly.This lattice only comprises one deck molecule, thereby it is regarded as individual layer.In addition near mode MN tensio-active agent individual layer 156 ' floating ' or ' drift ' that, a plurality of GaN molecule 1s 66 can similar liquid crystal.As shown in Fig. 2 A, form the N atomic plane of a plurality of GaN molecule 1s 66 towards gas phase 158, yet the Ga atomic plane that forms a plurality of GaN molecule 1s 66 is towards thin liquid metal wetting layer 154.In this respect, as mentioned above, a plurality of GaN molecule 1s 66 form tensio-active agents because they have a liking for that metal side (being Ga atom) faces thin liquid metal wetting layer 154 and their thin metal side (being N atom) faces gas phase 158.

Generally speaking, MN tensio-active agent individual layer 156 plays two independent effects.As active surface agent, MN tensio-active agent individual layer 156 reduces the surface tension of thin liquid metal wetting layer 154, thereby makes it flatten to simulate as ' sea (sea) ' as shown at Fig. 2 A and make the epitaxy as shown in following Fig. 2 B and 2C become possibility.In addition, as follows, MN tensio-active agent individual layer 156 use act on the precursor substance of the growth of the crystal 153 in nourishing (nourishing) growth.As mentioned above, according to disclosed technology, must regulate and keep the MN tensio-active agent individual layer 156 that shows with double-headed arrow 161 and the distance between the crystal 153 in growth so that the GaN molecule in MN tensio-active agent individual layer 156 can transition, tunnelling or diffused to the crystal 153 in growth.In addition, also must regulate and keep the thickness of MN tensio-active agent individual layer 156 to make to be no more than two or three individual layer (not shown)s be formed on thin liquid metal wetting layer 154 surfaces.Generally speaking, the metal that is introduced in the growing environment being shown in Fig. 2 A and the proper equilibrium between nonmetal composition are depended in aforesaid adjusting.

With reference now to the method for using Fig. 1 of the general reference 180 that builds and operate according to the another embodiment of disclosed technology, second schematic diagram Fig. 2 B of the atomic structure of metal-nonmetallic compound crystal of growing.By identical numbering, come signature 2A and element similar in 2B.Fig. 2 B shows that a GaN molecule 1 68 is how from 156 transition of MN tensio-active agent individual layer or tunnelling to solid phase 152.Generally speaking, set the temperature of the crystal 153 in growth lower than the temperature of a plurality of GaN molecule 1s 66 of wherein thin liquid metal wetting layer 154 solubilized.Therefore, the phasor (not shown) according to Ga metal melt (being thin liquid metal wetting layer 154) and GaN molecule (being a plurality of GaN molecule 1s 66), does not allow GaN molecule to appear in thin liquid metal wetting layer 154 on thermodynamics.Yet according to disclosed technology, if thin liquid metal wetting layer 154 has suitable thickness such as between one to three nanometer,, as shown in arrow 182, the mode that a GaN molecule 1 68 can be similar to the electron tunneling as known in quantum physics theory is from 156 transition of MN tensio-active agent individual layer, tunnelling or diffuse to solid phase 152.As shown in arrow 184, due to the kinetic energy that a GaN molecule 1 68 receives from one of a plurality of N atoms 162, can excite 68 transition of GaN molecule 1 or a tunnelling.Because the particle in gas phase 158 can have high-caliber kinetic energy, those particles beating and colliding on MN tensio-active agent individual layer 156 can cause that single GaN molecular transition or tunnelling are to solid phase 152.Because the crystal 153 in growth is by epitaxy, the crystal 153 in growth can show step-off construction such as showing by step (terrace) 186 in the crystal 153 in growth.Generally speaking, step representative favourable position of energy in growing crystal will be attracted and particularly coupling on step 186 of solid phase 152 the one GaN molecule 1 68.

With reference now to Fig. 1 method of using the general reference 200 that builds and operate according to another embodiment of disclosed technology, atomic structure schematic diagram Fig. 2 C of three metal-nonmetallic compound crystal of growing.Fig. 2 A, 2B are used identical numbering mark with the similar element in 2C.In Fig. 2 C, a GaN molecule 1 68 is with solid phase 152 couplings and add the crystal 153 in growth.As shown at Fig. 2 C, a GaN molecule 1 68 now has crystallographic configuration with the crystallography structure of the crystal 153 in coupling growth.Also in Fig. 2 C, show, another GaN molecule 204 has formed and has replaced the position of GaN molecule 1 68 in Fig. 2 A on MN tensio-active agent individual layer 156.In addition,, as shown in arrow 202, the 2nd GaN molecule 1 70 has started towards solid phase 152 transition and tunnelling.Also show that another Ga atom 206 enters MN tensio-active agent individual layer 156, wherein said Ga atom can and form another GaN molecule to be substituted in the 2nd GaN molecule in MN tensio-active agent individual layer 156 with the coupling of N atom.Because a GaN molecule is now located on the step in the crystal 153 in growth (unmarked), the 2nd GaN molecule 1 70 is by the GaN molecule 1 68 in the crystal 153 being attracted in growth.Generally speaking, once steering routine 100-106 (Fig. 1), just long-term steering routine 108 (Fig. 1) is continuously with continuous grown layer on crystal layer.As shown in Fig. 2 A-2C, the metallics in thin liquid metal wetting layer 154 and the nonmetal particle coupling in gas phase 158 to form MN molecule in MN tensio-active agent individual layer 156.Then MN molecular transition, the tunnelling in MN tensio-active agent individual layer 156 or diffuse to solid phase 152, thereby cause the growth as the crystal 153 in the growth of precursor substance extension.Then due to crystal 153 continued growths in growth, metal and nonmetal particle continue to be bonded in the MN molecule in MN tensio-active agent individual layer 156.

Refer back to Fig. 2 A, both must be conditioned MN tensio-active agent individual layer 156 and thin liquid metal wetting layer 154 and remain thin layer so that can grow according to the crystal 153 in disclosed technology growth.Thin liquid metal wetting layer 154 should not have the thickness and the MN tensio-active agent individual layer 156 that are greater than three nanometers should comprise no more than two to three individual layers, every layer of thickness with about 0.3 nanometer.Generally speaking, nearer between the crystal 153 in MN tensio-active agent individual layer 156 and growth, a plurality of GaN molecule 1s 66 should easier tunnelling to crystal 153 and GaN molecular transition in growth and should increase with the frequency of solid phase 152 couplings.Along with distance between solid phase 152 upper stratas (not marking) and MN tensio-active agent individual layer 156 increases, GaN molecule still less by tunnelling to solid phase 152.In addition, the particle in gas phase 158 can be combined with the particle in thin liquid metal wetting layer 154 on MN tensio-active agent individual layer 156, to form the other layer of metal-nonmetal molecule.For example, at the thickness of this other layer MN tensio-active agent individual layer 156 by be MN surfactant layer in the situation that, can be increased to two or three individual layers (not showing) in Fig. 2 A-2C in this way.Suppose under the thickness like this of two or three individual layers, surfactant layer by still have enough elasticity with form stable two-dimentional liquid crystal and the molecule in surfactant layer still can tunnelling to solid phase 152.

Yet, if the thickness that also increases surfactant layer such as four individual layers or more, it is unstable that surfactant layer can become, active agent layer manifests ctystallizing point surfacewise.So ctystallizing point can manifest any pressure that the uncommon angle to form between the molecule in surfactant layer in release surface active agent layer causes.These ctystallizing points can be to form on-right angle between the atom of relative short range and connection that can be in surfactant layer and molecule.This so can cause the atom of selected portion and the increase of molecular density of surfactant layer, described increase can cause snowslide (avalanche) crystallization.Then surfactant layer can become harder, and defect can in its structure, manifest and it finally can break.Then the polycrystal layer that embeds drop can manifest on the horizontal plane of surfactant layer, the epitaxy of this crystal 153 in can stopping growing.Thickness about thin liquid metal wetting layer 154 has also been supposed correlated results.If because the metallics being introduced in growing environment is too many, thin liquid metal wetting layer 154 becomes too thick, and the epitaxy of the crystal 153 in growing in the molecule from surfactant layer can stop and surfactant layer can be changed into polycrystal layer as above.In addition, too thin if thin liquid metal wetting layer 154 becomes, because thin liquid metal wetting layer 154 becomes dry, the epitaxy of the crystal 153 in growth can stop.As mentioned above, need to regulate both thickness of thin liquid metal wetting layer 154 and MN tensio-active agent individual layer 156 from the molecule of surfactant layer, to continue epitaxy to guarantee the crystal 153 in growth.

Also point out that MN tensio-active agent individual layer 156 can play the other effect that the drop on the crystal 153 in prevention growth forms.In using the prior art growing method of steam-solid growth technology growth crystal, be deposited on the formation that metal vapors on wafer or substrate causes drop on wafer or substrate surface, this can cause the defect of growing crystal.According to disclosed technology, owing to forming thin liquid metal wetting layer 154, MN tensio-active agent individual layer 156 forms substantially.MN tensio-active agent individual layer 156 play the thin liquid metal wetting layer 154 of neutralization surface can effect thereby the formation of prevention drop of active surface agent.This is due to the amphipathic character that forms the molecule of MN tensio-active agent individual layer 156.Be different from epitaxial film art methods (once wherein during growth technique expection have drop and then drop form need to take steps to eliminate them), according to disclosed technology because the formation of drop is avoided in the existence of MN surfactant layer.Metal and nonmetal particle form the surfactant layer molecule that substantially prevents drop to form substantially.

About gas phase 158, should point out to gas phase 158 thereby in MN surfactant layer 156, to form heterogeneity and precursor substance for the crystal 153 in growth by supply gas mixture.Thereby different substances can form the various layers of the crystal 153 in growth.Yet it will be understood by those skilled in the art that different gaseous mixture will have the efficiency in the crystal 153 from the MN molecule of gaseous mixture formation is extremely grown that is incorporated to of different levels.Different gaseous mixture also can affect MN molecule can transition and tunnelling to the easy degree in solid phase 152.

With reference now to Fig. 1 method of using the general reference 210 that builds and operate according to the another embodiment of disclosed technology, the 4th schematic diagram Fig. 2 D of the atomic structure of metal-nonmetallic compound crystal of growing.Fig. 2 D comprises solid phase 212, thin liquid metal wetting layer 214, MN tensio-active agent individual layer 216 and gas phase 218.Fig. 2 D shows after executed program 100-106 (Fig. 1), at thin liquid metal wetting layer and MN tensio-active agent the individual layer atomic structure after the top of crystal seed (metal that wherein forms thin liquid metal wetting layer is different from the metal in MN tensio-active agent individual layer) forms.Crystal 211 in solid phase 212 representative growths.In this schematic diagram, show SiC (silicon carbide) crystal that comprises a plurality of Si (silicon) atom 213 and a plurality of C (carbon) atom 215.As shown in the crystal 211 in growth, a plurality of Si atoms 213 and a plurality of C atom 215 are with crystallography structural arrangement.As shown, thin liquid metal wetting layer 214 comprises a plurality of Sn (tin) atom 217.MN tensio-active agent individual layer 216 comprises a plurality of SiC molecules 220 that are orientated (as by as shown in line 222) arrangement as learning with two dimensional crystal of tensio-active agent.Gas phase 218 comprises a plurality of SiC molecules 224.

The atomic structure being shown in Fig. 2 D can be prepared as follows.Solid phase 212 can be SiC seed wafer.Introduce SiC seed wafer to (not shown) in radio frequency (being abbreviated as RF herein) sputterer.Then the upper surface (unmarked) that uses the clean SiC seed wafer of argon plasma (not shown) rises to 250 ℃ by SiC seed wafer temperature simultaneously.Should point out that yet this temperature makes SiC molecule will be not dissolved in tin wetting layer higher than the fusing point of Sn lower than the liquidus temperature of SiC.By adding transformation with RF ripple in (biasing) SiC sputtering target, ar atmo will be the sputter of SiC molecule from SiC sputtering target (being shown as a plurality of SiC molecules 224).Simultaneously, open tin effusion cell (effusion cell) (not shown) coupling with RF sputterer and make to discharge for example one minute sufficiently long time of tin steam (not shown), thin liquid metal wetting layer 214 is formed on the surface of solid phase 212.Thin liquid metal wetting layer 214 can have the thickness of an about nanometer.As mentioned above, wetting layer is thin liquid tin wetting layer.A part for a plurality of SiC molecules 224 is adsorbed in the upper surface of thin liquid metal wetting layer 214, thereby a plurality of Sn atoms 217 is flattened and form MN tensio-active agent individual layer 216 (being shown as a plurality of SiC molecules 220).As shown in Fig. 2 D, each of a plurality of SiC molecules 220 all has its thin metal side (facing gas phase 218) of having a liking for metal side (facing a plurality of Sn atoms 217) and its a plurality of C atoms 215 of formation that forms a plurality of Si atoms 213.

Do not change the sputtering condition of RF sputterer, the SiC molecule in gas phase 218 will collide and clash into a plurality of SiC molecules 220 of a part that is MN tensio-active agent individual layer 216.Collision to the SiC molecule in the MN tensio-active agent individual layer 216 in thin liquid metal wetting layer 214 can transition, tunnelling or is diffused to solid phase 212, thereby add the crystal 211 in growth, such as adding the SiC molecule 219 of the crystal 211 in growth or being about to add the SiC molecule 221 of the crystal 211 (as with as shown in arrow 223) in growth.Once SiC molecule leaves MN tensio-active agent individual layer 216, the SiC molecule in gas phase 218 can replace its position in MN tensio-active agent individual layer 216.

With reference now to the method for using the general reference 230 of the Fig. 1 that builds and operate according to another embodiment of disclosed technology, the schematic diagram Fig. 3 A that is used for the system of growing metal-nonmetallic compound crystal.System 230 comprises growth room 232, pedestal 234 and motor 236.Motor 236 couples with pedestal 234.Growth room 232 can be crucible.Motor 236 can reduce and rising growth room 232 in pedestal 234, for example as shown in arrow 248, motor 236 can reduce pedestal 234.Motor 236 is rotatable pedestal 234 (not showing in Fig. 3 A) also.System 230 representatives are for the system of a large amount of crystal of growing from a large amount of liquid metals.Crystal seed 238 is placed on pedestal 234.Crystal seed 238 self can be placed in substrate (not shown), and described substrate is placed on pedestal 234.Crystal seed 238 is placed on pedestal 234 and makes growing crystal surface 250 thereon face the reverse of pedestal 234.Growth room 232 has been full of metal melt 240 and has made metal melt 240 covering surfaces 250.Many known technologies can be used for being full of growth room 232 and continuing supplying metal melt 240Zhi growth room 232 with metal melt 240.Should point out if growth room 232 is embodied as crucible, need suitably to select the material of growth room 232 to make metal melt 240 under the temperature of fusion of metal melt 240 will not dissolve crucible to comprise metal melt 240.

Then provide nonmetal gas 242 to the growth room 232 on the surface of metal melt 240.The particle of nonmetal gas 242 and metal melt 240 will interact, thereby on the surface 250 of crystal seed 238, form metal-nonmetallic surface promoting agent individual layer 246.MN tensio-active agent individual layer 246 makes the upper strata of metal melt 240 flatten substantially.As shown in Fig. 3 A, regulate distance (being shown as line 244) to several nanometers between surface 250 and MN tensio-active agent individual layer 246 make MN molecular transition in MN tensio-active agent individual layer 246 tunnelling to surface 250 and start to form crystal on crystal seed 238.Can be by reducing or rising pedestal 234 and regulating as the distance with as shown in line 244 by the amount that adjusting is supplied to the metal melt 240 of growth room 232.For example, can from MN tensio-active agent individual layer 246, add the speed of the surface 250 of crystal seed 238 speed of epitaxial growth crystal (not shown) to reduce pedestal 234 corresponding to MN molecule, thus the distance that retention wire 244 shows.

Because the surface of crystal seed 238 that only faces MN tensio-active agent individual layer 246 is for growing crystal, system 230 can be used for growth flawless crystal substantially in a large number.For example, supposing the system 230 is for the single GaN crystal of growing.In this example, metal melt 240 will be that gallium melt and nonmetal gas 242 will be nitrogen or nitrogen plasma.Crystal seed 238 will be the zero defect nano-pillar (nanopillar) with the surface (surface of the first type is called m-plane and the surface of the second type is called c-plane) of at least two types.Surface 250 representatives can be nano-pillar crystal seed 238 one of six m-planes and surface 252 represents one of two c-planes of crystal seed 238.In this example, it is parallel with MN tensio-active agent individual layer 246 that crystal seed is placed in one of m-plane of making it on pedestal 234.Then can growing GaN zoned crystal in that m-plane of crystal seed 238.Then the thin zoned crystal 90-degree rotation and the growth that grow in one of the m-plane of nano-pillar can be continued in one of the c-of crystal seed plane.On the required surface of crystal seed, can repeat program described above until obtain enough large crystal seed.According to the amount of the time of growing gan crystal in one of m-plane at crystal seed 238, the flawless single GaN crystal substantially of can growing.One of c-plane that the square plate of this single GaN crystal is placed in to it is upper, the endless a large amount of GaN crystal substantially of then can growing.As mentioned above, the temperature of crystal seed 238 and metal melt 240 is lower than the required minimum temperature of GaN molecule of dissolving in Ga melt, thereby according to this example, with for example for the prior art of a large amount of GaN crystal of growing, compare under significant low temperature at 300 ℃, the GaN crystal that can grow a large amount of.

With reference now to the schematic diagram Fig. 3 B that uses Fig. 1 method of the general reference 260 that builds and operate according to the another embodiment of disclosed technology for another system of growing metal-nonmetallic compound crystal.System 260 comprises growth room 262, the first gas inlet 264 and the second gas inlet 266.Growth room 262 can be high vacuum growth room.System 260 representatives are for the system from film growing crystal (also referred to as thin film epitaxy).Crystal seed 272 is placed in growth room 262.But crystal seed 272 self is placed in substrate (not shown), and described substrate is placed in growth room 262.Growth room 262 has been full of metal vapors (showing with arrow 268) and nonmetal steam (showing with arrow 270) simultaneously.Metal vapors 268 and nonmetal steam 270 codepositions (unmarked) on the upper surface of crystal seed 272, thus form thin liquid metal wetting layer 274 simultaneously and comprise from the MN tensio-active agent individual layer 276 of the metal-nonmetal molecule of

metal vapors

268 and 270 formation of nonmetal steam.According to disclosed technology, the MN crystal thereby grow in the MN molecule tunnelling in MN tensio-active agent individual layer 276 to the surface of crystal seed 272 on crystal seed 272.Known method can be used for the amount of metal vapors 268 and nonmetal steam 270 in growth regulation chamber 262.Generally speaking, according to disclosed technology, when the growth procedure for system 260 starts, the concentration of metal vapors 268 should, higher than the equipotent concentration of the nonmetal steam 270 of growth room 262, make to form thin liquid metal wetting layer 274.For example, if need the liquid metal wetting layer of a nano thickness, when starting, need to supply 100 seconds with the other metal deposition rates of 0.1 dust per second growth procedure.After this can get back to the stoichiometric balance point between metal vapors and nonmetal steam.As mentioned above, need to regulate the thickness of thin liquid metal wetting layer 274 to make it at crystal growing period, according to disclosed technology, keep overall stability.As known in the art, at high temperature thin liquid metal wetting layer 274 can slowly be got back to vaporous body, thereby must compensate by increasing gradually metal vapors 268Zhi growth room 262 any loss of the thickness of thin liquid metal wetting layer 274.

With reference now to building according to another embodiment of disclosed technology and schematic diagram Fig. 4 A of the epitaxially grown crystal of the general reference 300 of operation.Fig. 4 A shows how in the individual layer of individual molecule and growing crystal coupling, to grow according to the crystal of disclosed technology growth.Fig. 4 A is presented at the epitaxially grown crystal (unmarked) in four different stepss.Four different stepss of mark are 302A, 302B, 302C and 302D successively.Show that each crystal comprises a plurality of square 304, wherein each square 304 repetitive pattern that represent in crystalline composition.Each square 304 can represent a molecule with crystal coupling.As shown in stage 302A, crystal show into crystal coupling the step 306 from tensio-active agent individual layer (not shown) tunnelling to the favourable site of energy of the molecule of crystal particularly.In stage 302B, molecule 308 with crystal coupling on step 306.In stage 302C, molecule 310 with the available step of the next one on the crystal coupling of (unmarked).In stage 302D, molecule 312 with the available step of the next one on the crystal coupling of (unmarked).As shown, due to the surface of the molecule tunnelling in tensio-active agent individual layer to growing crystal, molecule ground forms crystal one by one.This make crystal can be essentially no defect ground epitaxy.

With reference now to building according to the another embodiment of disclosed technology and schematic diagram Fig. 4 B of the epitaxially grown crystal that shows Manhattan structure of the general reference 330 of operation.Fig. 4 B is presented in three different stepss just at epitaxially grown crystal (unmarked).Three different stepss of mark are 332A, 332B and 332C successively.Show that each crystal comprises a plurality of square 346, wherein each square 346 repetitive pattern that represent in crystalline composition.Each square 346 molecule that can represent with crystal coupling.As shown in stage 332A, crystal comprises a plurality of peaks 334 and a plurality of paddy 336.Can use known technology etching crystal or rule to give it to crystal and be shown in the structure in stage 332A.According to disclosed technology, only has the crystal fragment on the upper strata that substantially approaches thin liquid metal wetting layer (not shown) by the molecule tunnelling continued growth of passing through from tensio-active agent individual layer (not shown).In stage 332B, a plurality of peaks 340 another numberator height of having grown, yet due to a plurality of paddy 338 from the upper strata of thin liquid metal wetting layer too away to such an extent as to can not make molecule tunnelling to the crystal of that part, a plurality of paddy 338 is growth also.In stage 332C, a plurality of peaks 342 another numberator height of having grown, yet due to a plurality of paddy 344 from the upper strata of thin liquid metal wetting layer too away from so that can not make molecule tunnelling to the crystal of that part, a plurality of paddy 344 is growth also.As mentioned above, regulate thin liquid metal wetting layer slightly higher than the top of a plurality of peaks 334,340 and 342.As clearly illustrated in stage 332C, disclosed technology makes it possible to growing crystal to form the passage Huo‘ street be scattered with a plurality of openings ' the Manhattan structure that comprises a plurality of peaks or thin-walled.The crystal of Fig. 4 B can show mesa structure (not shown).

With reference now to building according to another embodiment of disclosed technology and schematic diagram Fig. 4 C of the epitaxially grown crystal that shows nano thread structure of the general reference 360 of operation.Fig. 4 C shows a plurality of crystal seeds 364 of growth substrate 361 thereon.Fig. 4 C shows the three phases of the growth that is labeled as successively 362A, 362B and 362C.Substrate 361 can be crystallization or amorphous structure, and a plurality of crystal seed 364 is the crystallizations in structure.Substrate 361 shows at first as the taper geometry as shown in stage 362A, wherein shows a plurality of short cone that represents a plurality of crystal seeds 364.Substrate 361 can be etched or line to be created in the geometrical shape of crystal seed shown in stage 362A.According to disclosed technology, a plurality of short cone representatives add the favourable site of energy of a plurality of crystal seeds 364 for the molecule from tensio-active agent individual layer (not shown).The whole upper surface of substrate 361 is covered by thin liquid metal wetting layer (not shown), yet only have the peak of a plurality of crystal seeds 364 to grow, because their the most approaching tensio-active agent individual layer (not shown)s that is positioned at the top of thin liquid metal wetting layer.As shown in stage 362B and 362C, a plurality of crystal seeds 364 grow into respectively a plurality of

nano wires

366 and 368, wherein the adjusting of thin liquid metal wetting layer promote from the molecule of tensio-active agent individual layer only with the peak coupling of a plurality of short cones.As in Fig. 4 B, the growth at a plurality of short cones peak leaves paddy (unmarked) or the open passage of a plurality of distributions.

Refer back to Fig. 1 and 2 A-2C, disclosed technology provides many novel purposes and crystalline structure that can be grown.For example, disclosed technology is used in the upper growing single-crystal structure of unconventional substrate (such as the substrate that shows crooked or round as a ball surface).Because the pressure of homogeneous will be present in whole CVD growth room, comprise curved surface, the method for Fig. 1 can use together with middle YaCVD growth room with on curved surface as crystalline fibers or there is the optical quartz crystal growing epitaxial layers of crystal seed.Use the method for Fig. 1 in crystalline fibers, can grow with the selected tinsel of nonmetallic ingredient codeposition for the surface of wetting crystalline fibers (program 102 of Fig. 1 and 104 both).After this, by changing the sedimentation rate of selected metal, can reach the stoichiometric balance point (program 106 of Fig. 1) of the growth of padded surface active agent layer, thereby the crystal in crystalline fibers can extension successively be grown.As another example, because the metal mixture of Y (yttrium), Ba (barium) and Cu (copper) has relative low eutectic melting point, can use the disclosed technology YBa that grows at low temperatures in sapphire crystalline fibers ₂cu ₃o ₇high temperature (being abbreviated as HTc herein) superconductor.As another example, the Seed Layer of can growing on silica fiber under the condition of steam solid when existing without tinsel with regard to silica fiber.Then use the method for Fig. 1, can increase metal deposition rates to form tinsel and wetting metal layer higher than stoichiometric balance point thereby in Seed Layer.Then, can reduce metal deposition rates to stoichiometric balance point thereby make nano-pillar to grow and to prolong and bear silica fiber in radial direction.

As mentioned above, disclosed technology makes at the significantly lower temperature of the art methods than for single crystal growing soon can growth table to reveal the crystal of single crystal structure.The growth temperature of using in disclosed technology in principle only can be slightly higher than the metal of introducing in program 102 (Fig. 1) or the temperature of fusion of metal mixture.For example at 2050 ℃, use prior art bavin according to disclosed technology, can at 680 ℃, grow by Laski (Czochralski) method growing sapphire (for alpha-alumina crystals).

In addition, disclosed technology make only can the to grow specific plane of crystal seed makes to select the particular crystal of growth to be orientated.As above Fig. 2 A-2C explains, the precursor substance of growing for crystal according to disclosed technology is the MN molecule that is positioned at the MN tensio-active agent individual layer of near distance relative to seed surface substantially.Therefore, according to disclosed technology, only will experience crystal growth with the crystal seed plane of the relative near distance of MN tensio-active agent individual layer.In the art methods of crystal growth (as growing crystal from metal melt or from growth from solution crystal), crystal seed is immersed in liquid and makes precursor molecule approach crystal seed from all sides.In these art methods, crystal is grown according to the growth velocity natural, thermodynamics regulation of each surface of crystal seed or plane.Use disclosed technology, on thermodynamics, do not allow active precursor molecule to approach the crystal growth from side or any side plane except next-door neighbour's tensio-active agent individual layer.This difference makes to can be used for the specific plane of the crystal of particular crystal application can be grown.For example, the m-plane of GaN is particularly useful in building transistor, because it does not show any piezoelectric properties that attract high electric field that are unfavorable for hall mobility.According to disclosed technology, can cut by this way and prepare crystal seed: required plane such as the m-plane in GaN will and next-door neighbour parallel with tensio-active agent individual layer.With regard to the prior art MBE method for crystal growth, although unidirectional supply precursor substance and at that specific direction growing crystal only, when using known MBE method growing nano post, the atoms metal in approaching can and growth in any coupling of crystal and can between the nano-pillar in paddy, deposit.This may cause the thickening of side crystal growth and nano-pillar.Very high temperature can be avoided this problem in these prior aries MBE method.According to disclosed technology, even at lower temperature, avoid the crystal growth in nano-pillar paddy, because precursor substance is only deposited on the upper surface of the nano-pillar of next-door neighbour's tensio-active agent individual layer.

Disclosed technology makes it possible under desirable condition the crystal that growth has the high quality crystal of zero defect or dislocation substantially.Generally speaking, due to the precursor molecule in approaching can be in growth the crystal surface of crystal on drift and float to them and be incorporated on the best site in the growth lattice of crystalline structure, the crystal growth in liquid is that method such as MBE tranquil and that grow than other crystal still less depends on temperature substantially.In growth lattice, this optimum position of precursor substance causes the high quality monolayer of crystal growth and thereby finally causes good crystal.As described above, disclosed technology makes it possible to reach growing crystal in the environment of stoichiometric balance point in liquid and between precursor substance.Generally speaking, technology provides as disclosed, more easily reaches stoichiometric balance point in liquid.As known, in being rich in the environment of gallium, be grown in GaN film and the nano-pillar of the electro-optical of the extra best best that can better control in liquid growing environment.

Also according to disclosed technology, multicomponent alloy can be used in crystal growth and the crystal of growth also can be doped.For example, because metal mixture is tending towards having eutectic melting point, ternary alloy can be used as the precursor substance of crystal growth under low temperature such as indium gallium nitride and selenizing zinc chrome.According to disclosed technology, the non-metallic atom and the particle that are used as precursor substance can be also that complex compound is such as arsenic phosphorus gallium or zinc oxide telluride (zinc oxide telluride).Therefore, disclosed technology provides the very uncommon metal of a kind of use and nonmetallic compound to carry out the method for growing crystal.In addition, the growth surface of precursor substance and crystal approaching makes to be easier to the growth surface doping that has the semiconductor film of n-type or p-type impurity to being.In addition, adulterate and substantially reduce the heat budget of crystal at low temperatures to growth surface, described heat budget conventionally causes the high diffusion length of dopant and also affects the desired concn of dopant.

According to another embodiment of disclosed technology, the different layers of the crystal of growth can comprise different compositions and different gradient or precursor substance from one deck to the conversion of one deck.For example, use disclosed technology Al ₂o ₃the first layer that crystal seed (aluminum oxide) can be used for growing AIN (aluminium nitride) is then the second layer of GaN.By controlling the sedimentation rate of each metal, can transform every layer to another layer, thereby can gradate AlN layer to GaN layer and maybe can in strong mode, transform AlN layer by changing the sedimentation rate of aluminium or gallium.Generally speaking, thus the various layers that are growths about the only restriction of this embodiment of disclosed technology should have similar crystalline network avoids misfit dislocation in the crystal of growth.According to this embodiment, the tensio-active agent individual layer of the precursor substance of growing as crystal can be changed gradually so that have the film of the composition of classification and can be grown.By changing the sedimentation rate of every layer, can change metal and the nonmetallic precursor substance that forms tensio-active agent individual layer.The film like this with the composition of classification can be used for building the direct band-gap semicondictor of classification.So semi-conductor can be used for collecting the wide spectrum sun power of solar radiation, is wherein present in each color in solar radiation and collects by the layer having in the semi-conductor of corresponding band gap.The example of this layer can comprise having general formula such as In _xga _1-xn, Al _xga _l-xas, GaAs _xn _1-xdeng individual layer.In other example of disclosed technology, yet should having similar crystalline network, the various layers of growth can promote misfit dislocation with growing nano post.

Disclosed technology also makes it possible to the uncommon crystalline structure of growing at low and stable temperature.For example, when by MBE method deposition InGaN (indium gallium nitride), because GaN dissociates at 800 ℃, InN (indium nitride) dissociates at 550 ℃, must be noted that system growth temperature.At low temperatures, extension will can not occur and at high temperature due to InN will dissociate it will can not be incorporated to growth lattice in.Use disclosed technology, can be at 50 ℃ growing InGaN.Therefore, according to disclosed technology, owing to avoiding, the temperature of some alloys and mixts is incompatible, the new precursor substance not being regarded as for crystal growth can be grown for crystal.

Because disclosed technology can be used for hetero epitaxy ground growing crystal, disclosed technology also makes it possible to the heterojunction crystal structure of growing.For example, about film growth system (as above Fig. 3 B is shown), can different time with various types of nonmetal particles such as the first nitrogen then the last arsenide of phosphorus thin liquid metal wetting layer is provided.Different nonmetal particles will change the composition of tensio-active agent individual layer, this so that will change the component of the crystal of growth, thereby make it possible to allos extension.As another example, can the thin liquid metal wetting layer of given metal be become dry and then can deposit on the crystal of the new thin liquid metal wetting layer being formed by different metal in growth according to disclosed technology.Alternatively, can introduce different metals to growing environment and just the liquid metal wetting layer of deposition of thin on crystal seed so that can allos extension.As mentioned above, the various layers of the crystal growth of growing on crystal seed can be able to be dried, the new crystal layer of can growing after drying, or given crystal layer can make by changing the precursor MN molecule of tensio-active agent individual layer its composition change.

As above Fig. 4 B and 4C describe, and disclosed technology makes it possible to grow the crystal of novel texture such as nano-pillar or Manhattan structure.Use prior art crystal technique, when using the precursor substance of liquid state or gaseous form as thin film deposition on the crystal seed with plane surface not time, film is conventionally consistent with the topological framework of plane surface not and cause uneven growing crystal.As described above, although owing to using the more atom of the method and particle to be deposited, the paddy that any nano-pillar of growth starts between the nano-pillar of thickening and growth starts to fill up, however the growth that MBE method and CVD method can cause showing the crystal growth of taper geometry and can cause nano-pillar.According to disclosed technology, because precursor molecule is by only transition or tunnelling are near adjacently situated surfaces tensio-active agent individual layer, the paddy between the nano-pillar of growth is held without particle precipitation.

It will be understood by those skilled in the art that disclosed technology is not limited to the content that specifically shows and describe as above in this paper.The scope of contrary disclosed technology is only defined by the claim as appended.

Claims (according to the modification of the 19th of treaty)

1. for the method for the tensio-active agent crystal growth from metal-nonmetal (MN) compound, it comprises following program:

Crystal seed is provided;

The atom of introducing the first metal to described crystal seed to form thin liquid metal wetting layer at least one surface of described crystal seed;

The temperature of setting described crystal seed is lower than for dissolving the required minimum temperature of MN molecule at described thin liquid metal wetting layer and higher than the fusing point of described the first metal, and described in each, MN molecule is formed by least one bimetallic atom and at least one first nonmetallic atom;

Introduce the described MN molecule that forms MN tensio-active agent individual layer, thereby promote the formation of described thin liquid metal wetting layer between described at least one surface of described MN tensio-active agent individual layer and described crystal seed; With

Regulate the thickness of described thin liquid metal wetting layer to make described at least one the surperficial coupling of MN molecule and described crystal seed described at least some of described MN tensio-active agent individual layer, thus the epitaxial film of the described MN compound of growing on described crystal seed.

2. method according to claim 1, its described program that also comprises described first nonmetallic described at least one atom of gasification is until form described MN tensio-active agent individual layer.

3. method according to claim 1, it also comprises that sputter MN compound target is for introducing the described program of the described MN molecule that forms described MN tensio-active agent individual layer.

4. method according to claim 1, it also comprises that gasification MN precursor is for introducing the described program of the described MN molecule that forms described MN tensio-active agent individual layer.

5. method according to claim 1, wherein from the 3rd metal and the described crystal seed of the second nonmetal formation.

6. method according to claim 5, wherein said the first metal, described the second metal and described the 3rd metal are identical.

7. method according to claim 5, wherein said the first metal, described the second metal and described the 3rd metal are different.

8. method according to claim 5, at least two in wherein said the first metal, described the second metal and described the 3rd metal is identical.

9. method according to claim 5, wherein said first nonmetal and described second nonmetal be identical.

10. method according to claim 5, wherein said first nonmetal and described second nonmetal be different.

11. methods according to claim 1, wherein said the first metal and described the second metal are respectively naturally from the metallic element of the described periodic table of elements, and described metallic element is classified as the freely metal of the following list forming of choosing:

Basic metal;

Alkaline-earth metal;

Transition metal;

Lanthanon;

Actinide elements; With

Other metal.

12. methods according to claim 1, wherein said first nonmetal be non-metallic element from the periodic table of elements, described non-metallic element is classified as the freely following list forming nonmetal of choosing:

Nonmetal; With

Halogen.

13. methods according to claim 1, the freely following list forming of wherein said crystal seed choosing:

The homogeneous crystal relevant to described MN compound;

The heterocrystal relevant to described MN compound;

Little crystallite at amorphous Grown; With

The little crystallite of growing in crystalline substrate.

14. methods according to claim 1, wherein said crystal seed shows the freely crystallography structure of the following list forming of choosing:

Step-off construction;

Manhattan structure;

Nano thread structure;

Flat geometry; With

Pyramidal structure.

15. methods according to claim 1, the described program of wherein introducing described MN molecule comprises uses crystal technique in the required growing environment of the described MN compound of growth, to introduce the sub-routine of precursor substance.

16. methods according to claim 15, the freely following list forming of wherein said crystal technique choosing:

Chemical vapour deposition (CVD);

Molecular beam epitaxy (MBE);

Rheotaxy (LPE);

Vapour phase epitaxy (VPE); With

Solution growth.

17. methods according to claim 1, the described program of wherein introducing the atom of described the first metal comprises the freely sub-routine of the following list forming of choosing:

Using described atom as the most condensing in described at least one lip-deep steam introducing of described crystal seed;

Described atom is introduced as described at least one the surperficial liquid metal that surrounds described crystal seed; With

The compound that introducing comprises described the first metal and non-metallic element, wherein said compound is dissociated near described crystal seed.

18. methods according to claim 1, the described program of wherein introducing described MN molecule comprises the sub-routine of codeposition metallics and nonmetal particle, described metallics and nonmetal particle combination are to form described MN molecule.

19. methods according to claim 1, wherein regulate the described program of described thickness to comprise the freely sub-routine of the following list forming of choosing:

Use evaporation controller to regulate described thickness for controlling the vaporator rate of described MN molecule;

Use gas inlet pressure warning unit and spectrophotometer to regulate described thickness; With

Use drop standard and refletcion high-energy electron diffraction (RHEED) technology to regulate described thickness.

20. methods according to claim 1, the described program of wherein setting described temperature comprises the sub-routine of the optimum temps of measuring described crystal seed, wherein maximizes the stoichiometric balance point that is incorporated to speed and adjustable MN precursor substance of described MN molecule.

21. methods according to claim 1, it also comprises following program:

The described atom that stops introducing described the first metal parches described thin liquid metal wetting layer; With

On described crystal seed, be grown in the crystal layer that shows the described MN compound of polycrystalline structure on the described epitaxial film of described MN compound.

22. methods according to claim 1, it also comprises following program;

Being introduced into of described the first nonmetallic atom of slowing down is essentially no, thereby on the described epitaxial film of MN compound, leaves the thin layer of the described atom of described the first metal; With

Remove the described thin layer of the described atom of described the first metal.

23. methods according to claim 22, wherein said removal program comprises the freely sub-routine of the following list forming of choosing:

By heating described crystal seed, evaporate described thin layer;

With thin layer described in wet-chemical technique etching; With

Thin layer described in the etching of use plasma chemistry technology.

24. methods according to claim 1, the freely following list forming of wherein said crystal seed choosing:

The crystallization seed of nano-scale;

The seed of huge mm size;

There is at least one flat surperficial wafer;

The wafer with crystalline fibers tip;

Crystal seed with crystalline material coupling; With

Crystal seed with amorphous substance coupling.

25. methods according to claim 1, wherein said thin liquid metal wetting layer is a part of surrounding the metallic solution of described crystal seed.

26. methods according to claim 1, wherein said thin liquid metal wetting layer has the thickness up to 3 nanometers.

27. methods according to claim 1, wherein said MN tensio-active agent individual layer comprises up to three individual layers, and each of described three individual layers has the thickness of 0.3 nanometer substantially.

28. methods according to claim 1, the described program of wherein introducing the described atom of described the first metal is included near the described atom of the introducing of described crystal seed.

29. methods according to claim 1, the described program of wherein introducing the described atom of described the first metal comprises introduces described atom to contact with described crystal seed.

30. in growth room from the method for the tensio-active agent crystal growth of the metal from metal melt-nonmetal (MN) compound, described growth room comprises and is positioned at the pedestal of inside, described growth room and the motor coupling with described pedestal, for the described pedestal in mobile described growth room, it comprises following program:

Crystal seed is placed in and on described pedestal, makes the growth surface of described crystal seed face the direction back to described pedestal;

Described growth room is full of to described metal melt makes described growth surface be covered by the thin layer of described metal melt;

Introduce nonmetal gas to the described growth room on the surface of described metal melt, the particle of wherein said nonmetal gas and the particle interaction of described metal melt, thus form MN tensio-active agent individual layer; With

Regulate distance between described growth surface and described MN tensio-active agent individual layer to make molecule tunnelling in described MN tensio-active agent individual layer to described growth surface, thus on described growth surface at least one crystal layer of epitaxy.

31. methods according to claim 30, wherein move described pedestal by described motor and regulate described distance that described growth surface is covered by the described thin layer of described metal melt.

32. methods according to claim 30, wherein regulate described distance that described growth surface is covered by the described thin layer of described metal melt by adjusting the amount of metal melt described in described growth room.

33. for always from the method for the epitaxial crystal growth of the tensio-active agent of metal-nonmetal (MN) compound of growth room's film, described growth room comprises the first gas inlet coupling with described growth room, to introduce metal vapors to described growth room, with the second gas inlet coupling with described growth room, to introduce nonmetal steam to described growth room, it comprises following program;

Crystal seed is placed in to described growth room;

Described growth room is full of to described metal vapors and described nonmetal steam simultaneously, make described metal vapors and described nonmetal steam codeposition on the growth surface of described crystal seed, thereby described metal vapors and MN tensio-active agent individual layer on described thin liquid metal wetting layer form thin liquid metal wetting layer; With

Regulate the thickness of described thin liquid metal wetting layer to make MN molecule tunnelling in described MN tensio-active agent individual layer to described growth surface, thus on described growth surface at least one crystal layer of epitaxy,

The concentration of wherein said metal vapors makes to form described thin liquid metal wetting layer higher than the concentration of described nonmetal steam at first.

34. methods according to claim 33, wherein adjust the described concentration of described metal vapors to regulate the described thickness of described thin liquid metal wetting layer.

Claims

Crystal seed is provided;

The atom of introducing the first metal contacts at least one surface of described crystal seed, to form thin liquid metal wetting layer with described crystal seed;

Basic metal;

Alkaline-earth metal;

Transition metal;

Lanthanon;

Actinide elements; With

Other metal.

Nonmetal; With

Halogen.

The homogeneous crystal relevant to described MN compound;

The heterocrystal relevant to described MN compound;

Little crystallite at amorphous Grown; With

The little crystallite of growing in crystalline substrate.

Step-off construction;

Manhattan structure;

Nano thread structure;

Flat geometry; With

Pyramidal structure.

Chemical vapour deposition (CVD);

Molecular beam epitaxy (MBE);

Rheotaxy (LPE);

Vapour phase epitaxy (VPE); With

Solution growth.

21. methods according to claim 1, it also comprises following program:

22. methods according to claim 1, it also comprises following program;

By heating described crystal seed, evaporate described thin layer;

With thin layer described in wet-chemical technique etching; With

Thin layer described in the etching of use plasma chemistry technology.

The crystallization seed of nano-scale;

The seed of huge mm size;

There is at least one flat surperficial wafer;

The wafer with crystalline fibers tip;

Crystal seed with crystalline material coupling; With

Crystal seed with amorphous substance coupling.

28. methods for the tensio-active agent crystal growth from metal-nonmetal (MN) compound, it comprises following program:

Crystal seed is provided;

Near described crystal seed, introduce the atom of the first metal, to form thin liquid metal wetting layer at least one surface of described crystal seed;

The temperature of setting described crystal seed is lower than dissolving the required minimum temperature of MN molecule and higher than the fusing point of described the first metal in described thin liquid metal wetting layer, and described in each, MN molecule is formed by bimetallic at least one atom and first nonmetallic at least one atom;

Introduce the described MN molecule that forms MN tensio-active agent individual layer, thereby promote to form described thin liquid metal wetting layer between described at least one surface of described MN tensio-active agent individual layer and described crystal seed; With

Regulate the thickness of described thin liquid metal wetting layer to make the described MN molecule of MN tensio-active agent individual layer and described at least one surperficial coupling of described crystal seed described at least some, thus the epitaxial film of the described MN compound of growing on described crystal seed.

The system of 29. growths of the tensio-active agent crystal for the metal from from metal melt-nonmetal (MN) compound:

Growth room;

Be positioned at the pedestal of inside, described growth room; With

The motor coupling with described pedestal, for the described pedestal in mobile described growth room,

Wherein crystal seed is placed in and on described pedestal, makes the growth surface of described crystal seed face the direction back to described pedestal;

Wherein said growth room is full of described metal melt described growth surface is covered by the thin layer of described metal melt;

Wherein introduce nonmetal gas to the described growth room on the surface of described metal melt;

The particle of wherein said nonmetal gas and the particle interaction of described metal melt, thus MN tensio-active agent individual layer formed; With

Wherein regulate distance between described growth surface and described MN tensio-active agent individual layer to make molecule tunnelling in described MN tensio-active agent individual layer to described growth surface, thus on described growth surface at least one crystal layer of epitaxy.

30. systems according to claim 29, wherein move described pedestal by described motor and regulate described distance that described growth surface is covered by the described thin layer of described metal melt.

31. systems according to claim 29, wherein regulate described distance that described growth surface is covered by the described thin layer of described metal melt by adjusting the amount of metal melt described in described growth room.

The system of the crystal growth of 32. tensio-active agents for the metal from from film-nonmetal (MN) compound, it comprises:

Growth room;

The first gas inlet coupling with described growth room, to introduce metal vapors to described growth room; With

The second gas inlet coupling with described growth room, to introduce nonmetal steam to described growth room,

Wherein crystal seed is placed in described growth room;

Wherein said growth room is full of described metal vapors and described nonmetal steam simultaneously, make described metal vapors and described nonmetal steam codeposition on the growth surface of described crystal seed, thereby described metal vapors and MN tensio-active agent individual layer on described thin liquid metal wetting layer form thin liquid metal wetting layer;

The concentration of wherein said metal vapors makes to form described thin liquid metal wetting layer higher than the concentration of described nonmetal steam at first; With

The thickness of wherein said thin liquid metal wetting layer is conditioned the MN molecule tunnelling that makes in described MN tensio-active agent individual layer to described growth surface, thus on described growth surface at least one crystal layer of epitaxy.

33. systems according to claim 32, wherein adjust the described concentration of described metal vapors to regulate the described thickness of described thin liquid metal wetting layer.